Methanol → Methyl 3-acetyl-5-bromo-4-hydroxybenzoate

HRID 1187165Notes

Reaction equation

HRID 1187165 reaction equation
[C:1]([C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([Br:14])[C:12]=1[OH:13])[C:7]([OH:9])=[O:8])(=[O:3])[CH3:2].S(Cl)(Cl)=O.[CH3:19]O>>[C:1]([C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([Br:14])[C:12]=1[OH:13])[C:7]([O:9][CH3:19])=[O:8])(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 887MethanolHCID 24386Thionyl ChlorideHCID 124864693-Acetyl-5-bromo-4-hydroxybenzoic acid

Product 1

HCID 15818980Methyl 3-acetyl-5-bromo-4-hydroxybenzoateYield 42.7%

Conditions

Temperature
80 °C

Procedure

To a stirred suspension of 3-acetyl-5-bromo-4-hydroxybenzoic acid (240 g, 926 mmol) in MeOH (2 L) was added dropwise sulfurous dichloride (68 mL, 926.5 mmol) under nitrogen and the mixture was heated at 80° C. for 3 h. The reaction mixture was cooled to room temperature concentrated, diluted with DCM. The organic layer was washed with brine, dried over magnesium sulfate, filtered and concentrated to afford a crude compound, which was purified on silica, eluting with 70% of DCM in petroleum ether. The solvents were evaporated to dryness to afford methyl 3-acetyl-5-bromo-4-hydroxybenzoate (108 g, 42.7%) as a white powder. Mass Spectrum: [M−H]− 229.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. concentrationconcentrated
  3. additiondiluted with DCM
  4. washThe organic layer was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto afford a crude compound, which
  9. customwas purified on silica
  10. washeluting with 70% of DCM in petroleum ether
  11. customThe solvents were evaporated to dryness

Sources & evidence

ORD record
ord-b972e7b05ca94911b708ea61f953cdf9
Source dataset
uspto-grants-2014_03
Patent number
US08673906B2

Reaction notes

Loading…